Analysis of organic electrode reactions by a thin layer electrochemical Raman method

在本计画中，我们首先发展了一种薄层电化学共振拉曼方法，分析了氯苯胺在金属阳离子存在下的还原过程。因此，在均匀溶液中和在电极表面上的反应之间的差异变得清楚。此外，我们还研究了碱土金属离子存在下四氰基醌二甲烷（TCNQ）的电化学还原过程。在乙腈中，有钡离子和镁离子存在时，TCNQ还原过程的循环伏安图表明，金属离子的存在对TCNQ还原形成自由基阴离子的过程没有影响，但对TCNQ还原形成二价阴离子的过程有较大的影响。在氧化扫描中，观察到两个氧化峰，这归因于吸附沉积物的脱附。从EQCM测量中可以看出，在电极表面上生长的是具有两个自由基阴离子的一个金属离子单元。并提出了以TCNQ二价阴离子的形成为关键步骤的含金属离子的自由基阴离子二聚体的结构生长模型。因此，为了确认二价阴离子的形成是结构生长的关键步骤，我们使用共振拉曼测量来分析存款。在514.5 nm激光激发下，从共振拉曼光谱中观察到TCNQ二价阴离子的氧化剂，从而证实了所提出的模型。在785 nm激光的激发下，还观察到了TCNQ自由基负离子的主要产物。

In this project, at first, we analyzed the reduction processes of chioranil in the presence of metal cations by developing a thin layer electrochemical resonance Raman method. Consequently, the differences in the reactions between in the homogeneous solutions and on the electrode surface have become clear. Also, the difference depending on the sort of metal cations has analyzed.In addition, we studied the electrochemical reduction process of tetracyanoquinodimethane (TCNQ) with the presence of the alkaline earth metal ion. Cyclic voltammogram of TCNQ reduction process with the presence of barium ion and magnesium ion in acetonitrile showed that the reduction process forming radical anion has no effect of the presence the metal ion, but the reduction process forming dianion has large effect of the metal ion. And in the oxidation scan, two oxidation peaks were observed which were attributed to desorption of adsorption deposits. From the EQCM measurement, it was appeared that the unit one metal ion with two radical anions grows on the electrode surface. And we could submit the structural growth model where radical anion dimer produced containing metal ion with the key step that forming TCNQ dianion. Therefore, to confirm the formation of dianion which is key step of the structural growth, we analyzed the deposit with using resonance Raman measurement. In the excitation using 514.5 nm laser, oxidant of TCNQ dianion was observed from the resonance Raman spectra, so the submitted model was confirmed. And also, in the excitation of 785 nm laser, TCNQ radical anion which was major product was observed.